CN1119639A - 一种邻-羟基苯乙酮的制备方法 - Google Patents
一种邻-羟基苯乙酮的制备方法 Download PDFInfo
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- CN1119639A CN1119639A CN94111457.0A CN94111457A CN1119639A CN 1119639 A CN1119639 A CN 1119639A CN 94111457 A CN94111457 A CN 94111457A CN 1119639 A CN1119639 A CN 1119639A
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- Prior art keywords
- acetophenone
- orthohydroxy
- hydroxy
- preparation
- ortho
- Prior art date
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- JECYUBVRTQDVAT-UHFFFAOYSA-N 2-acetylphenol Chemical compound CC(=O)C1=CC=CC=C1O JECYUBVRTQDVAT-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 title abstract description 13
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 21
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 9
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 3
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 abstract 2
- 239000003054 catalyst Substances 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 3
- 239000012346 acetyl chloride Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 150000004075 acetic anhydrides Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- MVPPADPHJFYWMZ-IDEBNGHGSA-N chlorobenzene Chemical group Cl[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 MVPPADPHJFYWMZ-IDEBNGHGSA-N 0.000 description 1
- 150000008422 chlorobenzenes Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- -1 leaves standstill Chemical compound 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
一种邻-羟基苯乙酮的制备方法,它以苯酚及乙酐为原料,以3-4摩尔比的三氯化铝为催化剂一步法制得邻-羟基苯乙酮和对-羟基苯乙酮,总产率为90.2%,邻-羟基苯乙酮的比例为80.5%,本方法工艺简单,邻位比例高。
Description
本发明涉及苯基酮的制备方法,特别是羟基苯基酮的制备方法。
邻-羟基苯乙酮是一种重要的化工原料,它可以用苯酚与乙酰氯在无水三氯化铝催化下经一步反应得到68.5%的邻-羟基苯乙酮和31.5%的对-羟基苯乙酮,总产率为89%(参见DE3108076)。该方法的缺点是用乙酰氯作原料,乙酰氯容易水解,处理很不方便,易污染环境。并且该法得到的邻-羟基苯乙酮的百分比尚不很高。
另外邻-羟基苯乙酮也可以用二步法制备:先将苯酚与乙酐反应生成酯,然后经Fries重排,得到邻-羟基苯乙酮和对-羟基苯乙酮,但邻-位产物只占总量的25%。(参见《化学试剂》,1993,15(4)254)。
本发明的目的是提供一种用苯酚和乙酐作为原料,得到邻位产物所占比例较高的一步法制备邻-羟基苯乙酮的方法。
本发明的技术解决方案是:将苯酚溶于对于F-C反应惰性的有机溶剂中,分批加入3—4摩尔比的无水三氯化铝,在加热、搅拌下,滴加入乙酐,反应完毕后,冷却至室温,反应混合物用盐酸冰水水解后,分出有机层,产物进行减压蒸馏即得邻-羟基苯乙酮和对-羟基苯乙酮,总产率为90.2%,邻位产物占80.5%。
本发明的方法所用的对于F-C反应惰性的有机溶剂可以是氯苯,1,2-二氯乙烷等,优选的溶剂是氯苯,反应温度控制在40~110℃之间,优选的温度是60~90℃。
本发明方法的优点是用乙酐作为酰化剂,一步法制备邻-羟基苯乙酮,处理方便,不易污染环境,总产率高,邻-位产物比例高。
以下通过实施例具体地说明本发明方法。
实施例:在1000毫升三颈瓶上装置电动搅拌器,温度计和Y型管。Y型管分别连接回流冷凝管和滴液漏斗,其上分别装有干燥管,回流冷凝管上的干燥管连接HCl气体吸收装置。
在三颈瓶中加入37.6克(0.40摩尔)苯酚,加入200毫升氯苯。称取170克(1.30摩尔)无水三氯化铝,取少量加入三颈瓶中,开动搅拌器。在滴液漏斗中加入50毫升(0.55摩尔)乙酐,缓慢滴加至反应瓶中,控制反应温度在40~50℃,反应过程中将170克三氯化铝分批加入(约70分钟加完)。乙酐滴加完毕后,将反应温度升至60~70℃,并在此温度下反应2小时。冷却,反应混合物在搅拌下用浓盐酸和碎冰的混合物水解,静置,分出有机层。水层用乙醚萃取。合并有机层和乙醚萃取液,依次用70毫升水,70毫升10%NaOH溶液,70毫升10%NaHCO3溶液,70毫升饱和NaCl溶液洗涤,用无水MgSO4干燥。
常压蒸去乙醚,然后减压蒸馏,得到微黄色油状的邻-羟基苯乙酮39.5克(bp.94—100℃/10mm)和微带红白色固态的对-羟基苯乙酮9.57克(bp.160一170℃/10mm,mp100—103℃)。
Claims (3)
1.一种邻-羟基苯乙酮的制备方法,它是将苯酚与乙酐在对于F-C反应惰性的有机溶剂中加热反应,其特征是使用3—4摩尔的三氯化铝作催化剂。
2.根据权利要求1所述的制备方法,其特征是优选的有机溶剂是氯苯。
3.根据权利要求1所述的制备方法,其特征是优选的反应温度是60~90℃。
Priority Applications (1)
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CN94111457.0A CN1119639A (zh) | 1994-09-27 | 1994-09-27 | 一种邻-羟基苯乙酮的制备方法 |
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CN94111457.0A CN1119639A (zh) | 1994-09-27 | 1994-09-27 | 一种邻-羟基苯乙酮的制备方法 |
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CN94111457.0A Pending CN1119639A (zh) | 1994-09-27 | 1994-09-27 | 一种邻-羟基苯乙酮的制备方法 |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102093189B (zh) * | 2009-12-09 | 2014-05-07 | 曹日庆 | 一种邻羟基苯乙酮和对羟基苯乙酮的制备方法 |
CN104910003A (zh) * | 2015-04-10 | 2015-09-16 | 渭南畅通药化科技有限公司 | 一种合成2,4-二羟基苯乙酮及废水回收再利用的方法 |
-
1994
- 1994-09-27 CN CN94111457.0A patent/CN1119639A/zh active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102093189B (zh) * | 2009-12-09 | 2014-05-07 | 曹日庆 | 一种邻羟基苯乙酮和对羟基苯乙酮的制备方法 |
CN104910003A (zh) * | 2015-04-10 | 2015-09-16 | 渭南畅通药化科技有限公司 | 一种合成2,4-二羟基苯乙酮及废水回收再利用的方法 |
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